US3413292A - Process for making tertiary amino ketones from the corresponding alcohols - Google Patents
Process for making tertiary amino ketones from the corresponding alcohols Download PDFInfo
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- US3413292A US3413292A US516734A US51673465A US3413292A US 3413292 A US3413292 A US 3413292A US 516734 A US516734 A US 516734A US 51673465 A US51673465 A US 51673465A US 3413292 A US3413292 A US 3413292A
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- percent
- catalyst
- tertiary amino
- amino ketones
- corresponding alcohols
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/10—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms
- C07D295/104—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/108—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
Definitions
- ABSTRACT OF THE DISCLOSURE Amino ketones can be produced from the corresponding secondary alcohol by contacting the alcohol in the vapor phase with a copper-containing catalyst.
- the secondary alcohol feedstock is represented by the formula R R OH N-CH-CH-R RI where R, R and R each is an organic group and R" is hydrogen or an organic gr0up,the organic groups being alkyl, aromatic or heterocyclic groups having 1 to 18 carbon atoms.
- This invention is directed to a method for the production of amino ketones. More particularly, this invention is directed to a new method for thecatalytic synthesis of amino ketones 'from amine alcohols.
- compounds of the general formula RR'NCI-IR"CHOHR"' are converted to compounds of the formula RR'NCHR"COR"' by catalytically contacting a feed compound in vapor phase with a reduced copper catalyst.
- R, R and R' are organic groups containing 1 to 18 carbon atoms suchas methyl, ethyl, propyl, isopropyl, fbutyl, phenyl, morpholino, anilino, dodecyl, dodecyl phenyl, etc.
- R" is either organic group as above defined or hydrogen.
- the catalyst to be used in accordance with the present invention is a copper catalyst such as a prereduced copper-chrome catalyst containing about 2 to about 75 wt. percent of chrome; for instance a copper-chrome-zinc catalyst containing from about 2 to about 25 wt. percent of chrome and about 93 to about 25 wt. percent of zinc (as oxides).
- a catalyst may be prepared by hydrogen reduction of a mixture containing 5 to 50 wt. percent of copper oxide and 2 to 25 wt. percent of chromium oxide with, correspondingly, 93 to 25 wt. percent of the zinc oxide.
- the reduction, accomplished in the presence of hydrogen may be conducted at a temperature within the range of 300 to 500 C. by passing a stream of a hydrogencontaining gas such as a mixture of 2 to mol percent of hydrogen with, correspondingly, 98 to 90 mol percent of nitrogen over the catalyst for a period of time within the range of 2 to 24 hours sufficient to substantially reduce the copper oxide to metallic copper. Under these conditions, the more difficultly reducible chromium oxide will remain in the oxide form.
- a hydrogencontaining gas such as a mixture of 2 to mol percent of hydrogen with, correspondingly, 98 to 90 mol percent of nitrogen
- tertiary amino alcohols in which the nitrogen can be part of an aliphatic, aromatic or heterocyclic system, are passed over a reduced copper catalyst 'at a temperature within the range of about 250 to about 400 C. in vapor phase at a flow rate of about 0.5 to about Patented Nov. 26, 1968 1 pound of feed per pound of catalyst per hour, dehydrogenation of the hydroxyl group occurs with the formation of a ketone corresponding to the original alcohol.
- the hydroxyl group should be beta to the nitrogen.
- the catalyst that was used was prepared from a mixture of 11 wt. percent copper oxide, 22 wt. percent chromia and 60 wt. percent zinc oxide. The catalyst was pelleted and reduced with a stream of 4 percent hydrogen and nitrogen for 20 hours at 380 to 400 C.
- Example I that morpholino-acetone (morpholino-propanone-Z) was produced in 93% yield with conversion of feed.
- Example II In a manner similar to that described in Example I, 2-hydroxybutylmorpholine was converted to morpholinobutanone-Z in 97% yield with 53% conversion of feed.
- Example III In a manner similar to that described in Example I, N-methylanilino-propanol-2 was converted to N-methylanilino-propanone-2 in 83% yield with 93% con-version of feed.
- Example IV In a manner similar to that described in Example I, diethylaminopropanol-2 was converted to diethylaminopropanone-2 in 86% yield with 91% conversion of feed.
- a method for the production of an amino ketone represented by the formula RR'NCHR"COR"' which comprises contacting a tertiary amino alcohol represented by the formula RR'NCHR"CHOHR" with a coppercontaining catalyst in vapor phase at a temperature within the range of about 250 to about 400 C., wherein R, R and R each is an organic group and R" is hydrogen or an organic group, said organic groups having from about 1 to about 18 carbon atoms and being selected from alkyl, aromatic or heterocyclic groups wherein the catalyst is obtained by the hydrogen reduction of a mixture of 5 to about 50 wt. percent of copper, about 2 to about 25 wt. percent of chrome and about 93 to about 25 wt. percent of zinc, all as oxides.
- tertiary amino alcohol is selected from Z-hydroxypropyl-N-methylaniline, 1-diethylamino-2-hydroxypropane, Z-hydroxypropylmorpholine and Z-hydroxybutylrnorpholine.
- NICHOLAS S. RIZZO Primary Examiner.
Description
United States Patent M Tex., assignors to Jefferson Chemical Company, Inc., a
corporation of Delaware No Drawing. Filed Dec. 27, 1965, Ser. No. 516,734 6 Claims. (Cl. 2602 47.7)
ABSTRACT OF THE DISCLOSURE Amino ketones can be produced from the corresponding secondary alcohol by contacting the alcohol in the vapor phase with a copper-containing catalyst. The secondary alcohol feedstock is represented by the formula R R OH N-CH-CH-R RI where R, R and R each is an organic group and R" is hydrogen or an organic gr0up,the organic groups being alkyl, aromatic or heterocyclic groups having 1 to 18 carbon atoms.
This invention is directed to a method for the production of amino ketones. More particularly, this invention is directed to a new method for thecatalytic synthesis of amino ketones 'from amine alcohols.
In accordance with the present invention, compounds of the general formula RR'NCI-IR"CHOHR"' are converted to compounds of the formula RR'NCHR"COR"' by catalytically contacting a feed compound in vapor phase with a reduced copper catalyst. In the above formulae, R, R and R' are organic groups containing 1 to 18 carbon atomssuchas methyl, ethyl, propyl, isopropyl, fbutyl, phenyl, morpholino, anilino, dodecyl, dodecyl phenyl, etc. R" is either organic group as above defined or hydrogen. Representative examples of suitable feedstocks which may be used in accordance with the present invention are 2-hydroxypropyl-N-methylaniline, 1 diethylamino 2 hydroxypropane, 2 hydroxypropylmorpholine, Z-hydroxybutylmorpholine, etc..
The catalyst to be used in accordance with the present invention is a copper catalyst such as a prereduced copper-chrome catalyst containing about 2 to about 75 wt. percent of chrome; for instance a copper-chrome-zinc catalyst containing from about 2 to about 25 wt. percent of chrome and about 93 to about 25 wt. percent of zinc (as oxides). As another example, a catalyst may be prepared by hydrogen reduction of a mixture containing 5 to 50 wt. percent of copper oxide and 2 to 25 wt. percent of chromium oxide with, correspondingly, 93 to 25 wt. percent of the zinc oxide.
The reduction, accomplished in the presence of hydrogen, may be conducted at a temperature within the range of 300 to 500 C. by passing a stream of a hydrogencontaining gas such as a mixture of 2 to mol percent of hydrogen with, correspondingly, 98 to 90 mol percent of nitrogen over the catalyst for a period of time within the range of 2 to 24 hours sufficient to substantially reduce the copper oxide to metallic copper. Under these conditions, the more difficultly reducible chromium oxide will remain in the oxide form.
When tertiary amino alcohols, in which the nitrogen can be part of an aliphatic, aromatic or heterocyclic system, are passed over a reduced copper catalyst 'at a temperature within the range of about 250 to about 400 C. in vapor phase at a flow rate of about 0.5 to about Patented Nov. 26, 1968 1 pound of feed per pound of catalyst per hour, dehydrogenation of the hydroxyl group occurs with the formation of a ketone corresponding to the original alcohol. For this synthesis, the hydroxyl group should be beta to the nitrogen. Thus, a wide variety of 'feedstocks may be employed In the following specific examples, the catalyst that was used was prepared from a mixture of 11 wt. percent copper oxide, 22 wt. percent chromia and 60 wt. percent zinc oxide. The catalyst was pelleted and reduced with a stream of 4 percent hydrogen and nitrogen for 20 hours at 380 to 400 C.
The invention will be further illustrated with respect to the following specific examples which are given by way of illustration and not as limitation on the scope of this invention. Where parts are given, they are parts by weight.
Example I that morpholino-acetone (morpholino-propanone-Z) was produced in 93% yield with conversion of feed.
Example II In a manner similar to that described in Example I, 2-hydroxybutylmorpholine was converted to morpholinobutanone-Z in 97% yield with 53% conversion of feed.
Example III In a manner similar to that described in Example I, N-methylanilino-propanol-2 was converted to N-methylanilino-propanone-2 in 83% yield with 93% con-version of feed.
Example IV In a manner similar to that described in Example I, diethylaminopropanol-2 was converted to diethylaminopropanone-2 in 86% yield with 91% conversion of feed.
What is claimed is: 1. A method for the production of an amino ketone represented by the formula RR'NCHR"COR"' which comprises contacting a tertiary amino alcohol represented by the formula RR'NCHR"CHOHR" with a coppercontaining catalyst in vapor phase at a temperature within the range of about 250 to about 400 C., wherein R, R and R each is an organic group and R" is hydrogen or an organic group, said organic groups having from about 1 to about 18 carbon atoms and being selected from alkyl, aromatic or heterocyclic groups wherein the catalyst is obtained by the hydrogen reduction of a mixture of 5 to about 50 wt. percent of copper, about 2 to about 25 wt. percent of chrome and about 93 to about 25 wt. percent of zinc, all as oxides.
2. A method as in claim 1 wherein the feed compound is 2-hydroxypropylmorpholine and the product is morpholino-propanone-2.
3. A method as in claim 1 wherein the feed compound is N-methylanilinopropanol-2 and the product is N- methylanilinopropanone-Z.
4. A method asin claim 1 wherein the feedstock is 4 diethylaminopropanol-Z and the product is diethylaminopropanone-Z. v
5. A method as in claim 1 wherein the feedstock is Z-hydroxybutylmorpholine and the product is morpholinobutanone-Z.
6. The method of claim 1 wherein the tertiary amino alcohol is selected from Z-hydroxypropyl-N-methylaniline, 1-diethylamino-2-hydroxypropane, Z-hydroxypropylmorpholine and Z-hydroxybutylrnorpholine.
No references cited.
NICHOLAS S. RIZZO, Primary Examiner.
JOSE TOVAR, Assistant Examiner.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US516734A US3413292A (en) | 1965-12-27 | 1965-12-27 | Process for making tertiary amino ketones from the corresponding alcohols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US516734A US3413292A (en) | 1965-12-27 | 1965-12-27 | Process for making tertiary amino ketones from the corresponding alcohols |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3413292A true US3413292A (en) | 1968-11-26 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US516734A Expired - Lifetime US3413292A (en) | 1965-12-27 | 1965-12-27 | Process for making tertiary amino ketones from the corresponding alcohols |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3413292A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0585682A2 (en) * | 1992-08-29 | 1994-03-09 | BASF Aktiengesellschaft | Process for the preparation of 2,6-dimethylmorpholine from N-(2-hydroxypropyl)-2,6-dimethylmorpholine |
| WO2008014965A1 (en) * | 2006-08-04 | 2008-02-07 | Clariant Finance (Bvi) Limited | Use of aminoacetones and salts thereof as bleaching boosters for peroxygen compounds |
-
1965
- 1965-12-27 US US516734A patent/US3413292A/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0585682A2 (en) * | 1992-08-29 | 1994-03-09 | BASF Aktiengesellschaft | Process for the preparation of 2,6-dimethylmorpholine from N-(2-hydroxypropyl)-2,6-dimethylmorpholine |
| EP0585682A3 (en) * | 1992-08-29 | 1994-06-15 | Basf Ag | Process for the preparation of 2,6-dimethylmorpholine from n-(2-hydroxypropyl)-2,6-dimethylmorpholine |
| US5436335A (en) * | 1992-08-29 | 1995-07-25 | Basf Aktiengesellschaft | Preparation of 2,6-dimethylmorpholine from N-(2-hydroxypropyl)-2,6-dimethylmorpholine |
| WO2008014965A1 (en) * | 2006-08-04 | 2008-02-07 | Clariant Finance (Bvi) Limited | Use of aminoacetones and salts thereof as bleaching boosters for peroxygen compounds |
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